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Femtosecond observation of benzyne intermediates in a molecular beam: Bergman rearrangement in the isolated molecule

Diau, Eric W.-G. and Casanova, Joseph and Roberts, John D. and Zewail, Ahmed H. (2000) Femtosecond observation of benzyne intermediates in a molecular beam: Bergman rearrangement in the isolated molecule. Proceedings of the National Academy of Sciences of the United States of America, 97 (4). pp. 1376-1379. ISSN 0027-8424. PMCID PMC26440. http://resolver.caltech.edu/CaltechAUTHORS:DIApnas00

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Abstract

In this communication, we report our femtosecond real-time observation of the dynamics for the three didehydrobenzene molecules (p-, m-, and o-benzyne) generated from 1,4-, 1,3-, and 1,2-dibromobenzene, respectively, in a molecular beam, by using femtosecond time-resolved mass spectrometry. The time required for the first and the second C-Br bond breakage is less than 100 fs; the benzyne molecules are produced within 100 fs and then decay with a lifetime of 400 ps or more. Density functional theory and high-level ab initio calculations are also reported herein to elucidate the energetics along the reaction path. We discuss the dynamics and possible reaction mechanisms for the disappearance of benzyne intermediates. Our effort focuses on the isolated molecule dynamics of the three isomers on the femtosecond time scale.


Item Type:Article
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http://www.pnas.org/content/97/4/1376.longPublisherArticle
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC26440/PubMed CentralArticle
Additional Information:© 2000, The National Academy of Sciences. Contributed by Ahmed H. Zewail, December 2, 1999. We thank Mr. Hans-Christian Becker for his helpful assistance and discussion. This work was supported by the U.S. Air Force Office of Scientific Research and the Office of Naval Research. Acknowledgement is also made to the donors of the Petroleum Research Fund administered by the American Chemical Society for support of this research. The publication costs of this article were defrayed in part by page charge payment. This article must therefore be hereby marked “advertisement” in accordance with 18 U.S.C. §1734 solely to indicate this fact. Article published online before print: Proc. Natl. Acad. Sci. USA, 10.1073/pnas.030524797. Article and publication date are at www.pnas.org/cgi/doi/10.1073/pnas.030524797
Funders:
Funding AgencyGrant Number
Air Force Office of Scientific Research (AFOSR)UNSPECIFIED
Office of Naval Research (ONR)UNSPECIFIED
American Chemical Society Petroleum Research FundUNSPECIFIED
Subject Keywords:DFT, density functional theory, PES, potential energy surface
PubMed Central ID:PMC26440
Record Number:CaltechAUTHORS:DIApnas00
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:DIApnas00
Alternative URL:http://dx.doi.org/10.1073/pnas.030524797
Official Citation:Eric W.-G. Diau, Joseph Casanova, John D. Roberts, and Ahmed H. Zewail Femtosecond observation of benzyne intermediates in a molecular beam: Bergman rearrangement in the isolated molecule PNAS 2000 97 (4) 1376-1379; published ahead of print January 31, 2000, doi:10.1073/pnas.030524797
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:511
Collection:CaltechAUTHORS
Deposited By: Archive Administrator
Deposited On:11 Jul 2005
Last Modified:19 Jul 2017 23:24

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